Cationic azo dyes from aminohalobenzenesulfonamides

ABSTRACT

NOVEL COMPOUND OF THE FORMULA   1-((4-(R2-N(-R3),Y-PHENYL)-N=N-),2-X,(N(+)(-R1)3-R-NH-SO2-   )-BENZENE Z(-)   WHEREIN R REPRESENTS LOWER ALKYLENE; R1 REPRESENTS LOWER ALKYL, BENZYL, OR ANY EQUIVALENTS THEREOF, AND EACH R1 MAY BE THE SAME OR DIFFERENT; R2 AND R3 MAY BE THE SAME OR DIFFERENT AND EACH REPRESENTS HYDROGEN, CYCLOALKYL, PHENYL, BENZYL, ENZYL SUBSTITUTED WITH LOWER ALKOXYCARBONYL, LOWER ALKYL OR LOWER ALKYL SUBSTITUTED WITH HALOGEN, CARBAMOYL, SUCCINIALKOXY, ACYLOXY, ALKANOYLAMIDO, CARBANOYL, SUCCINIMIDO, PHTHALIMIDO, OR R2 AND R3 WITH THE NITROGEN ATOM TO WHICH THEY ARE BONDED MAY BE COMBINED TO REPRESENT (-CH2-CH2-SO2-CH2-CH2-)&gt;N- OR (-CH2-CH2-O-CH2-CH2-)&gt;NY REPRESENTS HYDROGEN, LOWER ALKYL, ALKANOYLAMIDO, BENZAMIDO, OR LOWER ALKOXY; X REPRESENTS HALOGEN; AND Z REPRESENTS A BASIC DYE ANION. THESE DYES IMPART FAST YELLOW TO ED SHADES TO ACRYLIC, MODACRYLIC, ACID-MODIFIED POLYESTER AND ACID-MODIFIED POLYAMIDE FIBERS.

United States Patent 3,836,518 'CATIONIC AZO DYES FROM AMINOHALO-BENZENESULFONAMIDES Gary T. Clark, Kingsport, Tenn., assignor to EastmanKodak Company, Rochester, N.Y. No Drawing. Filed Mar. 9, 1972, Ser. No.233,299 Int. Cl. 00% 29/36; D06p 3/00 US. Cl. 260-152 9 Claims ABSTRACTOF THE DISCLOSURE Novel compounds of the formula wherein I' I l 'lNCHzCH1SO CH CH NCH;CH;OCH;CH:; Y represents hydrogen, lower alkyl,alkanoylamido, benzamido, or lower alkoxy; X represents halogen; and Zrepresents a basic dye anion.

These dyes impart fast yellow to red shades to acrylic, modacrylic,acid-modified polyester and acid-modified polyamide fibers.

This invention relates to novel cationic azo dyes and to the use of suchcompounds as dyes for acrylic, modacrylic, and acid-modified polyesterand acid-modified polyamide textile fibers, yarns and fabrics. Moreparticularly, this invention relates to cationic azo dyes derived fromaminohalobenzenesulfonamides and selected dialkylaniline couplers. Thesedyes impart fast yellow to red shades to acrylic, modacrylic,acid-modified polyester and acid-modified polyamide fibers. They haveparticularly good properties on acrylic and acid-modified polyamidefibers.

The novel cationic compounds of this invention have the general formula:

R represents lower alkylene; R represents lower alkyl, benzyl, or anyequivalents thereof such as morpholino, piperidino, etc., and each R maybe the same or different;

3,836,518 Patented Sept. 17, 1974 R and R may be the same or dilferentand each represents hydrogen, cycloalkyl, phenyl, benzyl, benzylsubstituted with lower alkoxycarbonyl, lower alkyl or lower alkylsubstituted with halogen, hydroxy, lower alkoxy, lower acyloxy, loweralkanoylamido, carbamoyl, succinimido, phthalimido, or

R and R, with the nitrogen atom to which they are bonded may be combinedto represent Y represents hydrogen, lower alkyl, lower alkanoylamido,benzamido, or lower alkoxy;

X represents halogen; and

Z represents a basic dye anion.

As used herein to describe a substituent containing an alkyl moiety, theword lower designates a carbon content of up to about four carbon atoms.

The cationic dyes of the invention impart yellow to red shades toacrylic, modacrylic, acid-modified polyester and acid-modified polyamidefibers. These dyes give level dyeings with good exhaustion from the dyebath and good build-up properties and afford bright shades of excellentwash, perspiration, and light-fastness, which are not photochromic orprototropic (change in shade with increased acidity), and which areinsensitive to pH variations.

Typical of the alkylene groups representative of R are methylene,ethylene, propylene, butylene and the like. Typical of the lower alkyland cycloalkyl groups represented by each of R and R are methyl, ethyl,propyl, isobutyl, cyclopentyl, cyclohexyl, etc. Typical of thesubstituted lower alkyl and substituted benzyl groups represented by Rand R are methoxyethyl, ethoxymethyl, propoxyethyl, chloroethyl,bromopropyl, acetoxy, butyryloxy, acetamido, propionamido, benzylsubstituted with methoxycar'bonyl, etc. Typical of the substituentsrepresented by Z are C1 Br I e omGsofi, cure-o 112F049. etc.

Y represents hydrogen, methyl, acetamido or benzamido; X representschlorine or bromine; and Z represents a basic dye anion.

The cationic compounds of this invention are prepared according towell-known procedures. Thus, the cationic compounds of the invention areprepared by first diazotizing an amine having the formula (II) x NR2S6zNH-RNR;)

2 and coupling the resulting diazonium salt with compounds having thegeneral formula 3 wherein R, R R R X, Y, and Z are defined above, toform a monoazo compound. The amines of Formula (II) and the couplingprocedures that can be used are well known in the art of dye chemistry.

The novel cationic compounds of the invention are then formed bytreating the monoazo compounds described above with an alkylating agentat elevated temperature with or without an inert solvent. Suitablealkylating agents that can be used are the dialkyl sulfates, the alkylhalides, the aralkyl halides, the alkyl esters of arylsulfonic acids,etc. Examples of such alkylating agents include dimethyl sulfate,diethyl sulfate, dipropyl sulfate, ethyl bromide, methyl iodide, ethyliodide, benzylchloride, benzylbromide, methyl p-toluene sulfonate, andethyl benzenesulfonate.

The particular basic dye anion represented by Z will depend upon themethod of isolation utilized and the particular quaternizing agentemployed. The anion does not aifect the utility of the cations of theinvention as dyes nor does it affect the dye afiinity of the cations forpolyacrylonitrile textile materials. When the compounds are used to dyepolyacrylonitrile textile material, the anion becomes associated with apositively-charged ion de rived from the polyacrylonitrile and it isremoved from the dye cation and the polyacrylonitrile textile material,either in the dye bath or in a subsequent washing of the dyedpolyacrylonitrile textile material. As is Well known in the art, thecation of a cationic azo dye is responsible for the color of thecompound and the particular anion associated with the cation is notimportant.

, The cationic compounds of this invention and their preparation arefurther illustrated by the following examples:

PREPARATION OF AMINOHALOSULFONAMIDES Example 1.Preparation of3,4-dichloro-N-y-dimethylaminopropylbenzenesulfonamide A solution of104.1 g. (0.425 mole) of 3,4-dichlorobenzenesulfonylchloride in 300 ml.of acetone is treated with 43.0 g. (0.425 mole) of3-dimethylaminopropylamine at 5 C. with stirring. After addition of theamine is completed, the reaction is allowed to attain room temperature.The resulting amine hydrochloride is collooted by filtration and washedwith acetone. The salt is dissolved in water and made basic withconcentrated ammonium hydroxide. The free amine is collected byfiltration, washed with water, and air-dried to yield 111.0 g. (84%) of3,4-dichloro-N-y-dimethylaminopropylbenzenesulfonamide, m.p. 91-95 C.

Example la.Preparation of4-amino3-chloro-N-ydimethylaminopropylbenzenesulfonamide An autoclave ischarged with 31.0 g. (0.1 mole) of 3,4-dichloro-N 'ydimethylaminopropylbenzenesulfonamide and 180 g. of concentratedammonium hydroxide and heated at 200 C. for 16 hrs. The product iscollected by filtration and recrystallized from benzene to yield 11.0 g.4-amino-3-chloro-N 'y dimethylaminopropylbenzene sulfonamide, mp 111-115C.

Example 2.Preparation of4-chlOrO-3-nitrO-N-ydimethylaminopropylbenzenesulfonamide A solution of192.0 g. (0.75 mole) of 4-chloro-3-nitrobenzenesulfonylchloride istreated with 76.6 g. (0.75 mole) of 3-dimethylaminopropylamine at 0-5 C.with stirring. The mixture is treated as described in Example 1 to give155.0 g. of 4-chloro-3-nitro-N-v-dimethylaminopropylbenzenesulfonamide,m.p. 95-97 C.

Example 2aPreparation of 3-amino-4-chloro-N-dimethylaminopropylbenzenesulfonamide An autoclave is charged with 70.0g. (0.218 mole) of 4-chloro-4-nitro- N 'ydimethylaminopropylbenzenesulfonamide, 500 ml. ethanol, 7.0 g. of 5%Pt/C, and 28 p.s.i. of hydrogen and heated at 50 C. until the uptake ofhydrogen ceases. The catalyst is removed by filtration and the solventis evaporated to yield 60.0 g. of 3-arnino-4-chloro-N-y-dimethylaminopropylbenzenesulfonamide.

Example 3 4-amino-3-chloro-N-p dimethylaminoethylbenzenesulfonamide isprepared by substituting Z-dimethylaminoethylamine for3-dimethylaminopropylamine in Example 1 and subsequently employing theprocedure in Example 1a.

Example 4 3-amino-4-chloro-N-B dimethylaminoethylbenzenesulfonamide isprepared by substituting Z-dimethylaminoethylamine for3-dimethylaminopropylamine in Example 2 and by employing the procedurein Example 2a.

PREPARATION OF CATIONIC MONOAZO DYES Example 5 A solution of 4.83 g.(0.02 mole) of 3-amino-4-chloro-N-y-dimethylaminopropylbenzenesulfonamide (prepared in Example 2a) in 20ml. of water containing 7 ml. of concentrated hydrochloric acid isdiazotized at 0-5 C., by addition of a solution of 1.44 g. of sodiumnitrite in 10 ml. of water. A portion (0.005 mole) of the above solutionis added with stirring to a solution of 1.3 g. (0.005 mole) ofN-ethyl-N-B-succinimido-ethyl-m-toluidine in 25 ml. of 1:5 acid (1 partpropionic acid to 5 parts acetic acid) at 010 C. The excess acid isneutralized by the addition of ammonium acetate. After coupling iscomplete, the mixture is drowned in ice water and then made basic withconcentrated ammonium hydroxide. The resulting monoazo compound iscollected by filtration, washed with water and air dried.

Example 5a CrHs Example 6 3 amino4-chloro-N-y-dimethylaminopropylbenzenesulfonamide from Example 2a isdiazotized in the same manner as described in Example 5 and coupled with(0.005 mole) of N-ethyl-N-fi-succinimidoethylaniline to yield thecorresponding monoazo compound.

Example 6a The dye from Example 6 is quaternized in the same manner asdescribed in Example 5a. The cationic dye imparts fast yellow shades toacrylic and acid-modified polyamide fibers. This dye has the followingstructure:

The compounds of the invention can be used for dyeing acid-modifiedpolyamide fibers, acrylic and modacrylic polymer fibers, yarns andfabrics giving a variety of fast yellow to red shades when appliedthereto by conventional dye methods. Acrylic textile materials are thosewhich consist of at least 85 percent acrylonitrile and modacrylictextile materials are those consisting of at least 35 percent but lessthan 85 percent acrylonitrile. The compounds of the invention also giveexcellent dyeings on acid-modified acrylic fibers described in US. Pats.2,837,500, 2,837,501 and 3,043,811. The novel compounds can also be usedto dye sulfonate-modified polyester fibers such as are described in US.Pat. 3,018,272. Examples of the textile materials that are dyed with thecompounds of the invention are those sold under the trade names Orlon,Orion 42, Verel, Acrilan, Dynel, Creslan and Dacron 64. In general, thecompounds, when used as dyes on the described textile materials, exhibitimproved fastness, for example, to washing, to alkaline perspiration,gas (atmospheric fumes) and sublimation.

Textile materials dyed by the compounds of the invention arecharacterized by containing at least about 35 percent combinedacrylonitrile units and up to about 95 percent acrylonitrile units, andmodified, for example, by 65-5 percent of vinyl pyridine units asdescribed in US. Pats. 2,990,393 and 3,014,008, or modified by 65-5percent of vinyl pyrrolidone units, for example, as described by US.Pat. 2,970,783, or modified with 65-5 percent acrylic ester ofacrylamide units as described in US. Pats. 2,879,253, 2,879,254 and2,838,470. Similar amounts of the other polymeric modifiers mentionedabove are also useful. A preferred group of the copolymers readilydyeable with the dyes of the invention are the modacrylic polymers suchas described in US. Pat. 2,831,826, composed of a mixture of (A) 70-95percent by weight of a copolymer of from 30-65 percent by weight ofvinylidene chloride or vinyl chloride and 70-35 percent by weight ofacrylonitrile, and (B) 30-5 percent by weight of a second polymer fromthe group consisting of (1) homopolymers of acrylamidic monomers of theformula wherein R is selected from the group consisting of hydrogen andmethyl, and R and R are selected from the group consisting of hydrogenand alkyl groups of 1-6 carbon atoms, (2) copolymers consisting of atleast two of said acrylamidic monomers, and (3) copolymers consisting ofat least 50 percent by weight of at least one of said acrylamidicmonomers and not more than 50 percent by weight of a polymerizablemonovinyl pyridine monomer.

Another type of modacrylic polymer that can be dyed with the compoundsof the invention is an acetone soluble mixture of (a) 70-95 percent byweight of a copolymer of 30-65 percent by weight of vinylidene chlorideand 70-35 percent by weight of acrylonitrile and (b) 30-5 percent byweight of an acrylamide homopolymer having the above formula wherein R Rand R are as described above. Specific polymers of that type contain70-95 percent by weight of (a) a copolymer of from 30-65 percent byweight of vinylidene chloride and 70-35 percent by weight ofacrylonitrile and (b) 30-5 percent by weight of a lowerN-alkylacrylamide polymer such as poly-N-methacrylamide,poly-N-isopropylacrylamide and poly-N-tertiarybutylacrylamide.

The following example illustrates one way in which the compounds of theinvention can be used to dye acrylonitrile polymer textile material:

Example 32 An amount of 0.1 g. of dye is dissolved by warming in 5 cc.of 2-methoxyethanol. A 2% aqueous solution of a nonionic surfactant,such as Igepal CA (a polymerized ethylene oxide-alkylphenol condensationproduct), is added slowly until a fine emulsion is obtained and then thedye mixture is brought to a volume of 200 cc. with warm water. Five cc.of a 5% aqueous solution of formic acid or acetic acid are added andthen 10 g. of fabric made from an acrylic fiber is entered and, in thecase of Orion 42 acrylic textile material, the dyeing is carried out atthe boil for one hour. In the case of materials made of Verel modacrylicfiber, the dye bath temperature should not exceed C. in order to avoiddamage to the fiber. The dyed material is then washed well with waterand dried.

Although this invention has been described in detail with particularreference to preferred embodiments thereof, it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

I claim:

1. Compounds having the structural formula wherein R represents loweralkylene;

R represents lower alkyl or benzyl, and each K, may be the same ordifferent;

R and R may be the same or diflferent and each represents hydrogen,cyclopentyl, cyclohexyl, phenyl, benzyl, benzyl substituted with loweralkoxycarbonyl, lower alkyl or lower alkyl substituted with chloro,bromo, hydroxy, lower alkoxy, acetoxy, lower alkanoylamido, carbamoyl,succinimido or phthalimido, with the proviso that at least one of R or Rrepresents lower alkyl substituted with succinimido or phthalimido;

Y represents hydrogen, lower alkyl, lower alkanoylamido,

benzamido, or lower alkoxy;

X represents halogen; and

Z represents a basic dye anion selected from the group consisting of C1Br I CH SO C10 e cut-403 CHa-i -O mrol and Y represents hydrogen,methyl, acetamido or benzamido;

and

X represents chlorine or bromine.

3. Compound according to Claim 2 having the formula 4. Compoundaccording to Claim 2 having the formula 1 1 12 5. Compound according toClaim 20 having the formula 8. Compound according to Claim 2 having theformula B1 CH3 /C2H6 O fi N=N-N J-CH, N=N- N 5 QB \C2H4N/ I a; f OS0zNHO3H N CH:1) 0-0111 8 omn-mm-n-wn Chena a ll NH-HI-CH: I

9 9. Compound according to Claim 2 having the formula CH 6. Compoundaccording to Claim 2 having the formula 3 /CH2C6H5 N=N N\ /C-cr-r, 1(3256 0 C2HAN 1 7/ N=N N -CH: S02NHC8H5NCH3 C- H;

\ I 8 ZS g e CzHr-N So2NH'C2ElN\CH3)a fi-CHZ References 6 UNITED STATESPATENTS Z 3,148,178 9/1964 Wallace ct a1 260-152 3,342,799 9/1967Wallace et a1. 260 152 7. Compound according to Claim 2 having theformula 3,349,076 10/ 1967 Weaver 260152 3,386,987 6/1968 Weaver et a1260152 C} 3,354,182 11/1967 Kiihne 6: a1. 260-152X l @1115 0 3,524,8428/1970 Grossmann 6t a1. 260-151 N=NN\ 15-016 3,661,886 5/1972 Hegcr260-156 FLOYD D. HIGEL, Primary Examiner S 0 2NH- C HaN\G2H5) CCH:

3 1', us. c1. X.R.

Z 841 R; 260165, 207, 207.1, 556 AR, 556 B

